CN116060081A - Silicon capturing catalyst and preparation method thereof - Google Patents

Silicon capturing catalyst and preparation method thereof Download PDF

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Publication number
CN116060081A
CN116060081A CN202111278929.7A CN202111278929A CN116060081A CN 116060081 A CN116060081 A CN 116060081A CN 202111278929 A CN202111278929 A CN 202111278929A CN 116060081 A CN116060081 A CN 116060081A
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catalyst
molecular sieve
silicon
roasting
hours
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刘丽
杨成敏
郭蓉
段为宇
姚运海
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Priority to CN202111278929.7A priority Critical patent/CN116060081A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a silicon capturing catalyst and a preparation method thereof, wherein alumina is used as a carrier, a molecular sieve and an active component are loaded on the carrier, the active component is an oxide of a VIB group metal and an oxide of a VIII group metal, and the molecular sieve is loaded on the outer surface of the catalyst. The catalyst is prepared by taking alumina powder and sulfide powder of VIB group metal as raw materials, obtaining a precursor, then impregnating VIII group metal salt, performing hydrothermal treatment on a molecular sieve precursor, drying and roasting. The catalyst of the invention enables the molecular sieve to be supported on the outer surface of the catalyst instead of being kneaded with a carrier, thereby being beneficial to improving the contact surface of the molecular sieve and active metal, increasing the contact probability of the molecular sieve and cyclosiloxane compounds and improving the silicon capturing capacity of the catalyst; the utilization rate of the molecular sieve is increased, so that the dosage of the molecular sieve is reduced, and the cost of the catalyst is reduced.

Description

Silicon capturing catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of oil product hydrogenation, in particular to a silicon capturing catalyst and a preparation method thereof.
Background
At present, a large number of delayed coking devices still treat heavy inferior oil in China, and a defoaming agent is used in the treatment process, so that products such as coking dry gas, coking naphtha, coking diesel oil and the like contain a certain amount of silicon, and the silicon poisons catalysts for subsequent treatment of coking products, so that the catalysts are permanently deactivated. Therefore, the silicon capturing catalyst is required to be filled in the hydrotreating process of the coking dry gas, the coking naphtha, the coking diesel oil and the like, and meanwhile, the silicon capturing catalyst has high silicon capturing capacity and certain hydrogenation activity. It has been found that the silicon type in the char product is mainly cyclosiloxane type compounds, and that the silicon is trapped on a silicon trapping catalyst, and that the silicon ring of the cyclosiloxane is opened, which requires a higher acidity of the silicon trapping catalyst.
CN201911020761.2 discloses a silicon catching agent and a preparation method thereof. The silicon catching agent comprises a carrier and a hydrogenation active component, wherein the hydrogenation active component comprises 0.3-18.3 wt% of VIB metal sulfide, 0.1-5.0 wt% of VIB metal oxide and 0.2-12.0 wt% of VIII metal oxide based on the total weight of the silicon catching agent. The preparation method of the silicon catching agent comprises the following steps: (1) Impregnating a catalyst carrier with an impregnating solution containing a VIB group metal, then drying, and vulcanizing the dried material; (2) Impregnating the vulcanized material obtained in the step (1) with impregnating solution containing metals of the VIB group and the VIII group, and then drying and roasting in inert atmosphere to obtain the silicon catching agent.
CN200910188090.0 discloses a coker naphtha silicon-catching agent and its application. The coked naphtha silicon-catching agent takes alumina as a carrier, silicon dioxide as an auxiliary agent, W, mo and Ni as hydrogenation components, the pore volume of the coked naphtha silicon-catching agent is 0.5-0.70 mL/g, and the specific surface area is 250-500m 2 Per gram, the content of hydrogenation component calculated as oxide is 1% to the upper20% and the acid content is 0.3-0.5 mmol/g.
Although many researchers have improved the silicon capacity of the silicon capturing agent by various methods and means, the problems of high preparation cost and poor silicon capturing capability still exist, the operation period of the device is influenced, and the silicon poisoning of the main catalyst is caused.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a silicon capturing catalyst and a preparation method thereof, and the catalyst not only has high silicon capturing capacity, but also has certain hydrogenation saturation capacity.
In the context of the present specification, the content of group VIII metal oxide on the group VIB metal oxide wafer was analyzed using CO-FTIR (carbon monoxide in situ infrared analysis). The measurement conditions of the CO-FTIR include: the catalyst is ground and pressed into self-supporting sheets with the diameter of 13mm, and the self-supporting sheets are placed on an in-situ cell sample rack. With 3.0% H 2 S is vulcanized for 3 hours at 320 ℃, then H 2 And cooling to room temperature in the S atmosphere, vacuumizing to 300 ℃, purifying for 2 hours, and carrying out CO adsorption under the condition of reducing the temperature by liquid nitrogen. Introducing a small amount of CO gas into the in-situ tank, and desorbing to 10 after adsorption balance is carried out for 30min -4 Pa. And collecting infrared spectrums before and after CO adsorption, wherein the difference spectrum of the infrared spectrums before and after CO adsorption is the infrared spectrum result of CO adsorption by the catalyst. The experiment adopts a Nicolet 6700 Fourier transform infrared spectrometer, the scanning times are 32 times, and the resolution is 4cm -1 ，4000~650cm -1 The detector was MCT/A measured.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the technical purpose of the first aspect of the present invention is to provide a silicon capturing catalyst, which uses alumina as a carrier, and supports molecular sieve and active components thereon, wherein the active components are oxides of group VIB metals and oxides of group VIII metals, and the molecular sieve accounts for 1-12wt%, preferably 1.5-8wt%, more preferably 2-6wt% based on the total weight of the catalyst; group VIB metals are 2-15%, preferably 5-10% by oxide, group VIII metals are 2-10%, preferably 4-8% by oxide; the content of the VIII family metal oxide on the VIB family metal oxide wafer is 60-100% of the VIII family metal oxide; the molecular sieve is supported on the outer surface of the catalyst.
Further, the pore volume of the silicon-capturing catalyst is 0.5-1.0mL/g, preferably 0.7-1.0mL/g; the specific surface area is 250-500m 2 Preferably 350-500m 2 /g; the amount of acid B is 0.05-0.3mmol/g, preferably 0.08-0.2mmol/g.
Further, the silicon capturing catalyst comprises 60-100% of the mole ratio of the group VIB metal to the group VIII metal to the group S metal, preferably 65-90%, more preferably 70-90%, and most preferably 80-90% when analyzed by CO-FTIR.
Further, the molecular sieve is at least one selected from the group consisting of a Y-type molecular sieve, a ZSM-5 molecular sieve, a beta-type molecular sieve and an MCM-41 molecular sieve.
Further, the molecular sieve is supported on the external surface of the catalyst, and/or the molecular sieve is supported on the VIB group metal oxide, and/or the molecular sieve is supported on the VIII group metal oxide, and/or the molecular sieve is supported on alumina.
Further, the group VIB metal oxide is molybdenum trioxide or/and tungsten trioxide, and the group VIII metal oxide is nickel oxide or/and cobalt oxide.
The technical purpose of the second aspect of the present invention is to provide a preparation method of the silicon capturing catalyst, comprising the following steps:
(1) Mixing alumina powder, sulfide powder of VIB group metal, peptizing agent and extrusion aid, extruding to form strips, drying and roasting to obtain a catalyst precursor A;
(2) Impregnating the catalyst precursor A in the step (1) with an impregnating solution containing a group VIII metal salt and an organic aid, and drying and roasting to obtain a catalyst precursor B.
(3) And (3) mixing the catalyst precursor B in the step (2) with a molecular sieve precursor, performing hydrothermal treatment, and drying and roasting to obtain the silicon capturing catalyst.
Further, the sulfide powder of the VIB group metal in the step (1) is molybdenum sulfide or/and tungsten sulfide.
Further, the peptizing agent and the extrusion aid in the step (1) are well known to those skilled in the art, and as a more specific embodiment, the peptizing agent is at least one selected from nitric acid, phosphoric acid or acetic acid, and the extrusion aid is at least one selected from starch and polyethylene glycol.
Further, the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃ and the drying time is 3-6 hours; the roasting conditions are as follows: in the air or oxygen atmosphere, the roasting temperature is 300-700 ℃ and the roasting time is 3-6 hours.
Further, the group VIII metal salt in the step (2) is nitrate, acetate or sulfate of a group VIII metal, and may be an isovolumetric impregnation mode, where the group VIII metal is Ni and/or Co.
Further, the organic auxiliary agent in the step (2) is an alcohol or an organic acid containing hydroxyl and/or carboxyl, wherein the number of carbon atoms is 3-10. Specifically, at least one selected from ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, malonic acid, succinic acid and glutaric acid.
Further, the drying conditions in the step (2) are as follows: the drying temperature is 90-200 ℃ and the drying time is 3-6 hours; the roasting conditions are as follows: in the air or oxygen atmosphere, the roasting temperature is 200-400 ℃ and the roasting time is 3-6 hours.
Further, the molecular sieve precursor in the step (3) is a gel formed by mixing a silicon source and/or an aluminum source, a precipitant, a template agent and water, and the preparation method is well known to those skilled in the art, and adopts a precipitation or sol-gel mode. The silicon source is one or more of sodium silicate, tetraethoxysilane, silica sol and chromatographic silica gel; the aluminum source is one or more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite; the precipitant is at least one of sodium hydroxide, ammonia water and potassium hydroxide; the template agent is one or more selected from cetyl trimethyl ammonium bromide, ethylenediamine, n-butylamine, tetrapropyl ammonium bromide, ethanol, tetraethylammonium hydroxide, tetraethylammonium bromide, triethylamine, di-n-propylamine, diisopropylamine and methylcellulose.
Further, the hydrothermal treatment conditions of step (3): the temperature is 90-200deg.C, the pressure is 0.1-2.0MPa, the pH is 7.5-9.0, and the time is 5-48 hr.
Further, the drying conditions in the step (3) are as follows: the drying temperature is 20-90 ℃ and the drying time is 4-16 hours; the roasting conditions are as follows: in the air or oxygen atmosphere, the roasting temperature is 300-500 ℃ and the roasting time is 2-6 hours.
The technical purpose of the third aspect of the invention is to provide the application of the silicon capturing catalyst, which is used for the hydrogenation process of various silicon-containing raw materials such as coking dry gas, coking naphtha, coking diesel oil and the like.
Compared with the prior art, the catalyst provided by the invention has the following advantages:
(1) According to the catalyst disclosed by the invention, the molecular sieve is added, and is supported on the outer surface of the catalyst instead of being kneaded with a carrier, so that on one hand, the contact surface of the molecular sieve and the active metal is favorably improved, the contact probability of the molecular sieve and the cyclosiloxane compound is favorably improved, the capability of the molecular sieve for providing H protons for ring-opening reaction is improved, the intermediate after ring opening is subjected to hydrodesiliconizing reaction with the active metal, and silicon is fixed to a silicon-capturing catalyst, so that the silicon-capturing capability of the catalyst is improved; on the other hand, the capability of providing H protons can be precisely controlled by controlling the type and the content of the molecular sieve, so that the activity of the molecular sieve can be regulated and controlled; the third aspect increases the utilization of the molecular sieve, thereby reducing the amount of molecular sieve used and reducing the cost of the catalyst.
(2) In the preparation method, the cheap molybdenum sulfide powder and the alumina powder are extruded to form strips, and the roasted molybdenum sulfide is converted into molybdenum oxide, so that the released sulfur trioxide can reduce the interaction between the molybdenum oxide and the alumina, simultaneously a large number of pore channels can be generated, the pore volume and the specific surface area of the carrier are increased, and the silicon containing capacity of the catalyst is improved; then dipping the mixed solution of the VIII family metal and the organic auxiliary agent, which is beneficial to weakening the interaction between the carrier and the active metal and improving the dispersity of the metal, and is beneficial to loading the carrier on the surface of the VIB family metal oxide and improving the hydrogenation activity of the catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The composition of the catalyst provided by the invention is characterized by combining inductively coupled plasma ICP and XPS energy spectrum, wherein the total content of VIB group metal and the total content of VIII group metal in the catalyst are firstly characterized by ICP, and then the content of metal elements with different valence states in the catalyst is quantitatively characterized by an XPS energy spectrometer.
The invention uses CO-FTIR (carbon monoxide in situ infrared analysis) to analyze the content of VIII family metal oxide on VIB family metal oxide wafer. The measurement conditions of the CO-FTIR include: the catalyst is ground and pressed into self-supporting sheets with the diameter of 13mm, and the self-supporting sheets are placed on an in-situ cell sample rack. With 3.0% H 2 S is vulcanized for 3 hours at 320 ℃, then H 2 And cooling to room temperature in the S atmosphere, vacuumizing to 300 ℃, purifying for 2 hours, and carrying out CO adsorption under the condition of reducing the temperature by liquid nitrogen. Introducing a small amount of CO gas into the in-situ tank, and desorbing to 10 after adsorption balance is carried out for 30min -4 Pa. And collecting infrared spectrums before and after CO adsorption, wherein the difference spectrum of the infrared spectrums before and after CO adsorption is the infrared spectrum result of CO adsorption by the catalyst. The experiment adopts a Nicolet 6700 Fourier transform infrared spectrometer, the scanning times are 32 times, and the resolution is 4cm -1 ，4000~650cm -1 The detector was MCT/A measured.
Example 1
(1) Uniformly mixing molybdenum sulfide with alumina powder, nitric acid, starch and deionized water, wherein the molybdenum sulfide: alumina powder: nitric acid: starch: deionized water in the mass ratio of 7 to 93 to 4 to 3 to 60, kneading, extruding and molding, drying at 110 ℃ for 3 hours, and roasting at 550 ℃ for 3 hours to obtain the catalyst precursor A.
(2) Nickel nitrate and glycerol solution were impregnated into the catalyst precursor a prepared in step (1), then dried at 110 ℃ for 3 hours, and calcined at 350 ℃ for 3 hours, catalyst precursor B.
(3) Dissolving sodium hydroxide and siliconAdding the gum, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (ethylenediamine): n (H) 2 O) =15:1:7:4:190, stirring to form a uniform sol, namely a precursor of the Y molecular sieve, mixing with the catalyst precursor B prepared in the step (2), and performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours, and roasting at 450 ℃ for 3 hours to obtain the silicon capturing catalyst C-1.
The silicon capturing catalyst C-1 comprises the following components in percentage by weight: moO (MoO) 3 6.3 percent of NiO, 4.1 percent of Y molecular sieve, 3.1 percent of Y molecular sieve and the balance of alumina carrier.
Example 2
(1) Uniformly mixing molybdenum sulfide with alumina powder, nitric acid, starch and deionized water, wherein the molybdenum sulfide: alumina powder: nitric acid: starch: deionized water in the mass ratio of 9 to 91 to 4 to 3 to 60, kneading, extruding and molding, drying at 110 ℃ for 3 hours, and roasting at 450 ℃ for 3 hours to obtain the catalyst precursor A.
(2) Nickel nitrate and ethylene glycol solution were impregnated into the catalyst precursor a prepared in step (1), then dried at 110 ℃ for 3 hours, and calcined at 250 ℃ for 3 hours, catalyst precursor B.
(3) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (n-butylamine): n (H) 2 O) =18:1:6:6:200, stirring to form a uniform sol, namely a precursor of the ZSM-5 molecular sieve, mixing with the catalyst precursor B prepared in the step (2), and performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 3 hours to obtain the silicon capturing catalyst C-2.
The silicon capturing catalyst C-2 comprises the following components in percentage by weight: moO (MoO) 3 8.1%, niO 4.6%, ZSM-5 molecular sieve 4.8% and alumina carrier for the rest.
Example 3
(1) Uniformly mixing molybdenum sulfide with alumina powder, nitric acid, starch and deionized water, wherein the molybdenum sulfide: alumina powder: nitric acid: starch: deionized water in the mass ratio of 10 to 90 to 4 to 3 to 60, kneading, extruding and molding, drying at 110 ℃ for 3 hours, and roasting at 450 ℃ for 3 hours to obtain the catalyst precursor A.
(2) Nickel nitrate and ethylene glycol solution were impregnated into the catalyst precursor a prepared in step (1), then dried at 110 ℃ for 3 hours, and calcined at 450 ℃ for 3 hours, catalyst precursor B.
(3) Dissolving sodium metaaluminate and sodium hydroxide into deionized water, then adding tetraethylammonium bromide, stirring vigorously, slowly dropwise adding silica sol, and aging for 3 hours, wherein the molar ratio of each component is n (SiO) 2 ):n(Al 2 O 3 ):n(Na 2 O) n (tetraethylammonium bromide) n (H) 2 O) =24:1:6:5.5:280, forming a precursor of the beta-type molecular sieve, then mixing with the catalyst precursor B prepared in the step (2), and then performing hydrothermal treatment for 10 hours under the conditions of 150 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 3 hours to obtain the silicon capturing catalyst C-3.
The silicon capturing catalyst C-3 comprises the following components in percentage by weight: moO (MoO) 3 9.6%, niO 4.8%, beta-type molecular sieve 5.0% and alumina carrier for the rest.
Example 4
(1) Uniformly mixing molybdenum sulfide with alumina powder, nitric acid, starch and deionized water, wherein the molybdenum sulfide: alumina powder: nitric acid: starch: deionized water in the mass ratio of 4:96:4:3:60, kneading, extruding, forming, drying at 150 ℃ for 3 hours, and roasting at 500 ℃ for 3 hours to obtain the catalyst precursor A.
(2) Nickel nitrate and glycerol solution were impregnated into the catalyst precursor a prepared in step (1), then dried at 90 ℃ for 3 hours, and calcined at 250 ℃ for 3 hours, catalyst precursor B.
(3) Mixing cetyl trimethyl ammonium bromide with sodium hydroxide, adding into deionized water, stirring, dropwise adding ethyl orthosilicate into the mixed solution, stirring for 30min, wherein the molar ratio of each component is n (SiO) 2 ):n(Na 2 O) n (hexadecyl trimethyl ammonium bromide) n (H) 2 O) =12:2:4:200, forming an MCM-41 molecular sieve precursor, then mixing with the catalyst precursor B prepared in step (2), and then performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa, and ph=8.0; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours, and roasting at 500 ℃ for 3 hours to obtain the silicon capturing catalyst C-4.
The silicon capturing catalyst C-4 comprises the following components in percentage by weight: moO (MoO) 3 3.7%, 2.1% NiO, 3.4% MCM-41 molecular sieve and the rest alumina carrier.
Example 5
(1) Uniformly mixing molybdenum sulfide with alumina powder, nitric acid, starch and deionized water, wherein the molybdenum sulfide: alumina powder: nitric acid: starch: deionized water in the mass ratio of 8 to 92 to 4 to 3 to 60, kneading, extruding and molding, drying at 120 ℃ for 3 hours, and roasting at 450 ℃ for 3 hours to obtain the catalyst precursor A.
(2) Cobalt nitrate and citric acid solution were impregnated into the catalyst precursor a prepared in step (1), then dried at 80 ℃ for 3 hours, and calcined at 350 ℃ for 3 hours, catalyst precursor B.
(3) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (ethylenediamine): n (H) 2 O) =15:1:7:4:190, stirring to form a uniform sol, namely a precursor of the Y molecular sieve, mixing with the catalyst precursor B prepared in the step (2), and performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 3 hours to obtain the silicon capturing catalyst C-5.
The silicon capturing catalyst C-5 comprises the following components in percentage by weight: moO (MoO) 3 7.8%, coO 4.1%, Y-type molecular sieve 4.8% and alumina carrier for the rest.
Example 6
(1) Uniformly mixing tungsten sulfide with alumina powder, nitric acid, starch and deionized water, wherein molybdenum sulfide: alumina powder: nitric acid: starch: deionized water in the mass ratio of 9 to 91 to 4 to 3 to 60, kneading, extruding and molding, drying at 110 ℃ for 3 hours, and roasting at 520 ℃ for 3 hours to obtain the catalyst precursor A.
(2) Nickel nitrate and ethylene glycol solution were impregnated into the catalyst precursor a prepared in step (1), then dried at 90 ℃ for 3 hours, and calcined at 200 ℃ for 3 hours, catalyst precursor B.
(3) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (n-butylamine): n (H) 2 O) =18:1:6:6:200, stirring to form a uniform sol, namely a precursor of the ZSM-5 molecular sieve, mixing with the catalyst precursor B prepared in the step (2), and performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 3 hours to obtain the silicon capturing catalyst C-6.
The silicon capturing catalyst C-6 comprises the following components in percentage by weight: WO (WO) 3 8.6%, niO 4.2%, ZSM-5 molecular sieve 4.8% and alumina carrier the rest.
Example 7
(1) Uniformly mixing tungsten sulfide with alumina powder, nitric acid, starch and deionized water, wherein molybdenum sulfide: alumina powder: nitric acid: starch: deionized water in the mass ratio of 8.2 to 91.8 to 4 to 3 to 60, kneading, extruding and molding, drying at 120 ℃ for 3 hours, and roasting at 450 ℃ for 3 hours to obtain the catalyst precursor A.
(2) Cobalt nitrate and glycerol solution were impregnated into the catalyst precursor a prepared in step (1), then dried at 100 ℃ for 3 hours, and calcined at 350 ℃ for 3 hours, catalyst precursor B.
(3) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (ethylenediamine): n (H) 2 O) =15:1:7:4:190, stirring to form a uniform sol, i.e. a precursor of the Y molecular sieve, mixing with the catalyst precursor B prepared in step (2), and then stirring at 150 ℃, 1.0MPa, ph=8.0Performing hydrothermal treatment under the piece for 10 hours; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours, and roasting at 520 ℃ for 3 hours to obtain the silicon capturing catalyst C-7.
The silicon capturing catalyst C-7 comprises the following components in percentage by weight: WO (WO) 3 7.9%, coO 4.2%, Y-type molecular sieve 4.8% and alumina carrier for the rest.
Comparative example 1
(1) Uniformly mixing a Y-type molecular sieve with alumina powder, nitric acid, starch and deionized water, wherein the Y-type molecular sieve is as follows: alumina powder: nitric acid: starch: the mass ratio of deionized water is 8:92:4:3:60, then kneading and extruding strips for molding, then drying at 80 ℃ for 10 hours, and roasting at 650 ℃ for 3 hours to obtain the modified alumina carrier.
(2) And (2) immersing the mixed solution of phosphomolybdic acid and nickel nitrate into the modified alumina carrier prepared in the step (1), drying at 120 ℃ for 3 hours, and roasting at 450 ℃ for 3 hours to obtain the silicon capturing catalyst DC-1.
The catalyst DC-1 comprises the following components in percentage by weight: moO (MoO) 3 8.1%, niO 4.8%, Y molecular sieve 4.8%, and alumina the rest.
Comparative example 2
(1) Uniformly mixing a Y-type molecular sieve with molybdenum oxide, alumina powder, nitric acid, starch and deionized water, wherein the Y-type molecular sieve is as follows: alumina powder: nitric acid: starch: the mass ratio of deionized water is 4.8:8.1:87.1:4:3:60, then kneading and extruding to form strips, then drying at 80 ℃ for 10 hours, and roasting at 650 ℃ for 3 hours to obtain the catalyst precursor.
(2) And (3) dipping the nickel nitrate solution into the catalyst precursor prepared in the step (1), drying at 90 ℃ for 3 hours, and roasting at 250 ℃ for 3 hours to obtain the silicon capturing catalyst DC-2.
The catalyst DC-2 comprises the following components in percentage by weight: moO (MoO) 3 7.7%, niO 4.2%, Y molecular sieve 4.6% and the balance alumina.
The C-1 to C-7 catalysts prepared in the above examples, the DC-1 to DC-2 catalysts prepared in the comparative examples were analyzed for the content of the group VIII metal oxide on the group VIB metal oxide wafer, and the physicochemical properties of the catalysts, and the analysis results are shown in Table 1.
Table 1.
Figure DEST_PATH_IMAGE001
Example 8
This example illustrates the silicon capture activity of the catalyst provided by the present invention for coker naphtha.
The raw oil for evaluation is coked naphtha raw material provided by a certain refinery for medium petrifaction, and the main properties are as follows: the sulfur content was 5460. Mu.g/g, the nitrogen content was 246. Mu.g/g, and the silicon content was 38. Mu.g/g. Catalysts C-1 to C-7, comparative examples DC-1 to DC-2 were evaluated for their ability to trap silicon, respectively, using a 200mL fixed bed hydrogenation unit. Wherein catalysts C-1 to C-7, comparative examples DC-1 and DC-2 were subjected to a pretreatment. The pre-vulcanization conditions were: using a catalyst containing 3wt% CS 2 Is used for aviation kerosene at an airspeed of 1.5h -1 The hydrogen oil volume ratio was 500:1 and the prevulcanization was carried out at an operating pressure of 4.0 MPa. The reaction conditions were evaluated as follows: the operating pressure is 3.0MPa, the reaction temperature is 260 ℃, the hydrogen/oil volume ratio is 200:1, and the volume space velocity is 6.0h -1 The evaluation results are shown in Table 2.
Table 2.
Figure 917721DEST_PATH_IMAGE002
As can be seen from Table 2, the silicon-capturing catalyst of the invention has high silicon-capturing capacity and high hydrogenation activity.

Claims (17)

1. The silicon capturing catalyst is characterized in that aluminum oxide is used as a carrier, a molecular sieve and an active component are loaded on the carrier, the active component is an oxide of a VIB group metal and an oxide of a VIII group metal, and the molecular sieve accounts for 1-12wt%, preferably 1.5-8wt%, more preferably 2-6wt% based on the total weight of the catalyst; group VIB metals are 2-15%, preferably 5-10% by oxide, group VIII metals are 2-10%, preferably 4-8% by oxide; the content of the VIII family metal oxide on the VIB family metal oxide wafer is 60-100% of the VIII family metal oxide; the molecular sieve is supported on the outer surface of the catalyst.
2. The silicon-trap catalyst according to claim 1, wherein the pore volume of the silicon-trap catalyst is 0.5-1.0mL/g and the specific surface area is 250-500m 2 The acid amount of the acid B is 0.05-0.3mmol/g.
3. The silicon-trap catalyst according to claim 1, characterized in that it comprises a group VIB metal-group VIII metal-S phase in a molar ratio of 60-100%, preferably 65% -90% of the group VIII metal when analyzed by CO-FTIR.
4. The silicon-trap catalyst according to claim 1, wherein the molecular sieve is selected from at least one of a Y-type molecular sieve, a ZSM-5 molecular sieve, a beta-type molecular sieve, and an MCM-41 molecular sieve.
5. The silicon-capturing catalyst according to claim 1, wherein the group VIB metal oxide is molybdenum trioxide or/and tungsten trioxide, and the group VIII metal oxide is nickel oxide or/and cobalt oxide.
6. The preparation method of the silicon capturing catalyst comprises the following steps:
(1) Mixing alumina powder, sulfide powder of VIB group metal, peptizing agent and extrusion aid, extruding to form strips, drying and roasting to obtain a catalyst precursor A;
(2) Impregnating the catalyst precursor A in the step (1) with an impregnating solution containing a VIII group metal salt and an organic additive, and drying and roasting to obtain a catalyst precursor B;
(3) And (3) mixing the catalyst precursor B in the step (2) with a molecular sieve precursor, performing hydrothermal treatment, and drying and roasting to obtain the silicon capturing catalyst.
7. The process of claim 6 wherein the molecular sieve comprises 1 to 12 wt.% of the total weight of the catalyst, the group VIB metal comprises 2 to 15 wt.% of the oxide, and the group VIII metal comprises 2 to 10 wt.% of the oxide, and the starting materials are added.
8. The process according to claim 6, wherein the sulfide powder of the group VIB metal in step (1) is molybdenum sulfide or/and tungsten sulfide.
9. The method according to claim 6, wherein the peptizing agent is at least one selected from nitric acid, phosphoric acid and acetic acid, and the extrusion aid is at least one selected from starch and polyethylene glycol.
10. The method of claim 6, wherein the drying conditions in step (1) are: the drying temperature is 90-200 ℃ and the drying time is 3-6 hours; the roasting conditions are as follows: in the air or oxygen atmosphere, the roasting temperature is 300-700 ℃ and the roasting time is 3-6 hours.
11. The method of claim 6, wherein the group VIII metal salt in step (2) is a nitrate, acetate or sulfate of a group VIII metal.
12. The method according to claim 6, wherein the organic aid in the step (2) is at least one selected from the group consisting of ethylene glycol, glycerol, butylene glycol, pentylene glycol, acetic acid, citric acid, malonic acid, succinic acid and glutaric acid.
13. The method according to claim 6, wherein the drying conditions in step (2) are: the drying temperature is 90-200 ℃ and the drying time is 3-6 hours; the roasting conditions are as follows: in the air or oxygen atmosphere, the roasting temperature is 200-400 ℃ and the roasting time is 3-6 hours.
14. The method of claim 6, wherein the molecular sieve precursor in step (3) is a gel formed by mixing a silicon source and/or an aluminum source, a precipitant, a template agent and water, and the molecular sieve is obtained by precipitation or sol-gel.
15. The method according to claim 6, wherein the hydrothermal treatment conditions in step (3) are as follows: the temperature is 90-200deg.C, the pressure is 0.1-2.0MPa, the pH is 7.5-9.0, and the time is 5-48 hr.
16. The method according to claim 6, wherein the drying conditions in step (3) are: the drying temperature is 20-90 ℃ and the drying time is 4-16 hours; the roasting conditions are as follows: in the air or oxygen atmosphere, the roasting temperature is 300-500 ℃ and the roasting time is 2-6 hours.
17. The use of the silicon capture catalyst of claim 1 in the hydrogenation of various silicon-containing feedstocks such as coker dry gas, coker naphtha, coker diesel, and the like.
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